Diastereoselective Au-Catalyzed Allene Cycloisomerizations to Highly Substituted Cyclopentenes
Ryan D Reeves1, Alicia M Phelps1, William A T Raimbach1
1Department of Chemistry, University of Wisconsin , Madison, Wisconsin 53706, United States.
Abstract:
Site- and regiocontrolled Au-catalyzed allene carbocyclizations furnish highly substituted cyclopentenes in >1:1 dr. Significant substitution on the substrate is tolerated, with potential to install five contiguous stereocenters after alkene functionalization. Major challenges include identifying a Au/Cu catalyst that controls both the relative rates of allene epimerization/cyclization and the facial selectivity in addition of a metal enolate to the allene. Experiments to achieve stereodivergent cyclizations and transform key cyclopentenes into useful synthetic building blocks are described.
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